Hamish H.-M. Yeung

Mechanical Tunability via Hydrogen Bonding in Metal-Organic Frameworks with the Perovskite Architecture

Two analogous metal-organic frameworks (MOFs) with the perovskite architecture, [C(NH2)3][Mn(HCOO)3] (1) and [(CH2)3NH2][Mn(HCOO)3] (2), exhibit significantly different mechanical properties. The marked difference is attributed to their distinct modes of hydrogen bonding between the A-site amine cation and the anionic framework. The stronger cross-linking hydrogen bonding in 1 gives rise to Youngs moduli and hardnesses that are up to twice those in 2, while the thermal expansion is substantially smaller. This study presents clear evidence that the mechanical properties of MOF materials can be substantially tuned via hydrogen-bonding interactions.

Layered inorganic-organic frameworks based on the 2,2-dimethylsuccinate ligand: Structural diversity and its effect on nanosheet exfoliation and magnetic properties

The structures of four new 2,2-dimethylsuccinate frameworks suitable for exfoliation into nanosheets using ultrasonication are reported. These hybrid compounds contain either monovalent (Li(+)) or divalent (Co(2+) and Zn(2+)) cations, and they all feature hydrophobically capped covalently bonded layers that only interact with each other via weak van der Waals forces. Critically this shows that the use of this dicarboxylate ligand generally yields two dimensional compounds suitable for simple and affordable nanosheet exfoliation. This extends the range of frameworks that can be exfoliated and highlights the 2,2-dimethylsuccinate ligand as an excellent versatile platform for the production of nanosheets. The topologies of the layers in each framework were found to vary significantly and this appears to have a significant effect on the relative size of the nanosheets produced; increased space between methyl groups and more extensive inorganic connectivity appears to favour the formation of thin nanosheets with larger lateral dimensions. Additionally the magnetic properties of two of these frameworks were examined, and it was found that both exhibit strong low dimensional antiferromagnetic coupling despite their well-separated layers preventing three dimensional magnetic order.

Isomer-Directed Structural Diversity and Its Effect on the Nanosheet Exfoliation and Magnetic Properties of 2,3-Dimethylsuccinate Hybrid Frameworks

The structures of seven new transition metal frameworks featuring Mn, Co, or Zn and either the meso or chiral D and L isomers of the 2,3-dimethylsuccinate ligand are reported. Frameworks that exhibit two-dimensional covalently bonded layers with weak interlayer interactions can be made with all three cations by incorporation of the chiral isomers of the 2,3-dimethylsuccinate ligand. The formation of such structures, suitable for the creation of nanosheets via exfoliation, is, however, not as ubiquitous as is the case with the 2,2-dimethylsuccinate frameworks since frameworks that incorporate the meso-2,3-dimethylsuccinate ligand form three-dimensional structures. This clear distinction between the formation of structures with covalent connectivity in two and three dimensions, depending on the choice of 2,3-dimethylsuccinate isomer, is due to the different conformations adopted by the backbone of the ligand. The chiral isomer prefers to adopt an arrangement with its methyl and carboxylate groups gauche to the neighboring functional groups of the same type, while the meso-ligand prefers to adopt trans geometry. A gauche-arrangement of the methyl groups places them on the same side of the ligand, making this geometry ideal for the formation of layered structures; a trans-relationship leads to the methyl groups being further apart, reducing their steric hindrance and making it easier to accommodate them within a three-dimensional structure. The ease of exfoliation of the layered frameworks is examined and compared to those of known transition metal 2,2-dimethylsuccinate frameworks by means of UV-vis spectroscopy. It is suggested that layered frameworks with more corrugated surfaces exfoliate more rapidly. The size, structure, and morphology of the exfoliated nanosheets are also characterized. The magnetic properties of the paramagnetic frameworks reveal that only the three dimensionally covalently bonded phases containing meso-2,3-DMS in trans-arrangements order magnetically. These frameworks are antiferromagnets at low temperatures, although the Co compound undergoes an unusual antiferromagnetic to ferromagnetic transition with increasing applied magnetic field.

In Situ Observation of Successive Crystallizations and Metastable Intermediates in the Formation of Metal–Organic Frameworks

Understanding the driving forces controlling crystallization is essential for the efficient synthesis and design of new materials, particularly metal-organic frameworks (MOFs), where mild solvothermal synthesis often allows access to various phases from the same reagents. Using high-energy in situ synchrotron X-ray powder diffraction, we monitor the crystallization of lithium tartrate MOFs, observing the successive crystallization and dissolution of three competing phases in one reaction. By determining rate constants and activation energies, we fully quantify the reaction energy landscape, gaining important predictive power for the choice of reaction conditions. Different reaction rates are explained by the structural relationships between the products and the reactants; larger changes in conformation result in higher activation energies. The methods we demonstrate can easily be applied to other materials, opening the door to a greater understanding of crystallization in general.

Detailed investigations of phase transitions and magnetic structure in Fe(III), Mn(II), Co(II) and Ni(II) 3,4,5-trihydroxybenzoate (gallate) dihydrates by neutron and X-ray diffraction.

The effect of cation valency on the complex structures of divalent and trivalent transition metal gallates has been examined using a combination of neutron and synchrotron X-ray powder diffraction, single-crystal X-ray diffraction and XANES spectroscopy. In the divalent frameworks, M(C(7)H(4)O(5))·2H(2)O (M = Mn, Co and Ni), it was found that charge balance was achieved via the presence of protons on the meta-hydroxyl groups. It was also established that these compounds undergo a discontinuous phase transition at lower temperatures, which is driven by the position of the extra-framework water molecules in these materials. By contrast, in the trivalent Fe gallate, Fe(C(7)H(3)O(5))·2H(2)O, it was found that the stronger bonding between the meta-hydroxy oxygen and the cations leads to a weakening of the bond between this oxygen and its proton. This is turn is thought to lead to stronger hydrogen bonding with the extra-framework water. The lattice water is disordered in the Fe(III) case, which prevents the phase transition found in the M(II) gallates. Refinement against the neutron diffraction patterns also revealed that the relatively mild microwave synthesis of gallate frameworks in D(2)O led to an extensive deuteration of the ortho-hydrogen sites on the aromatic ring, which may suggest a more versatile method of deuterating aromatic organics. The antiferromagnetic structure of Co gallate has also been determined.

Structural diversity and luminescent properties of lanthanide 2,2- and 2,3-dimethylsuccinate frameworks

The structures of fourteen new lanthanide frameworks (La, Ce, Eu, Tb, Y and Lu) containing the 2,2- or 2,3-dimethylsuccinate ligands are reported. While the majority of the known 2,2-dimethylsuccinate frameworks feature two dimensionally bonded layers, capped by hydrophobic methyl groups, several of these new frameworks adopt quite different architectures. These include one dimensional inorganically connected chains (La and Ce) with only non-covalent interactions in the other two dimensions, and three dimensional covalently bonded frameworks (Eu and Lu) with spaces in their structure to accommodate the bulky methyl groups. The new 2,3-dimethylsuccinate frameworks (La and Y) adopt three-dimensional covalently bonded frameworks. The factors affecting the formation of structures with different dimensionalities are examined and compared to previously reported transition metal frameworks. In addition, the sequence of phases formed with changing lanthanide size, concentrations and temperatures are rationalised. The luminescent properties of several 1- and 2-D frameworks doped with Eu and Tb are reported, with the Y host exhibiting the most intense emission.

Ligand‐Directed Control over Crystal Structures of Inorganic–Organic Frameworks and Formation of Solid Solutions

Grounded in fact: Inorganic-organic frameworks with 3D Li-O-Li connectivity can form solid solutions through mechanochemical synthesis. High-resolution synchrotron powder X-ray diffraction and cross-polarization solid-state NMR spectroscopy demonstrate complete ligand mixing in the resulting binary and ternary systems (see picture for trends in unit cell volume (V) of the ternary system {Li2(suc)x(mal)y(met)z} n).

Coordination environments and π-conjugation in dense lithium coordination polymers

The understanding of lithium–oxygen coordination systems is important for making better lithium conductors as well as active materials for lithium ion batteries. Here, we report a systematic investigation on coordination environments in lithium coordination polymers (LCPs) through the syntheses and analyses of six new crystals composed of lithium ions and anthraquinone (aq) derivative anions, where the negative charges are distributed in π-conjugation systems. Their structures were determined by single-crystal X-ray diffraction to be (1) [Li2(23dcaq)(H2O)] in space group P21/c, (2) [Li(23dcaqH)] in P21/c, (3) [Li2(15dhaq)(H2O)2] in P21/c, (4) [Li2(14dhaq)(H2O)2] in Pnma, (5) [Li(14dhaqH)(H2O)] in P212121 and (6) [Li(14hnaq)(H2O)] in P212121 (23dcaq2− = 2,3-dicarboxy-aq, 14dhaq2− = 1,4-dihydroxy-aq, 15dhaq2− = 1,5-dihydroxy-aq and 14hnaq− = 1-hydroxy-4-nitro-aq). Through the comprehensive structure analysis of these materials as well as other LCPs, we found that when considering the longest C–O bond in the π-conjugation system of an anionic organic molecule and its coordination to a Li ion, there is a weak inverse relationship between the C–O and Li–O bond lengths. In addition, despite exhibiting optical band edges below 2 eV and 1D π-stacking connectivity, conductivity measurements on single crystals of 1–6 confirmed that they are all electronic insulators. We rationalize this finding on the basis of π-orbital delocalization, which is more restricted in the aq-based LCPs compared to known semiconducting hybrid materials.

Mechanical Properties of a Calcium Dietary Supplement, Calcium Fumarate Trihydrate

The mechanical properties of calcium fumarate trihydrate, a 1D coordination polymer considered for use as a calcium source for food and beverage enrichment, have been determined via nanoindentation and high-pressure X-ray diffraction with single crystals. The nanoindentation studies reveal that the elastic modulus (16.7-33.4 GPa, depending on crystallographic orientation), hardness (1.05-1.36 GPa), yield stress (0.70-0.90 GPa), and creep behavior (0.8-5.8 nm/s) can be rationalized in view of the anisotropic crystal structure; factors include the directionality of the inorganic Ca-O-Ca chain and hydrogen bonding, as well as the orientation of the fumarate ligands. High-pressure single-crystal X-ray diffraction studies show a bulk modulus of ∼ 20 GPa, which is indicative of elastic recovery intermediate between small molecule drug crystals and inorganic pharmaceutical ingredients. The combined use of nanoindentation and high-pressure X-ray diffraction techniques provides a complementary experimental approach for probing the critical mechanical properties related to tableting of these dietary supplements.

Phase behaviour of lithium tartrate framework isomers: kinetic and thermodynamic effects

Inorganic-organic frameworks have been the subject of great interest for several decades, including much recent research into metalorganic frameworks, coordination polymers and other similar materials. Composed of inorganic moieties connected by organic linkers, they form 1-, 2and 3-D architectures with intriguing properties that arise from the combination of their constituent parts.[1] Perhaps the most diverse group of inorganic-organic frameworks is based on the tartaric acid ligand, (C4H6O6), due to its conformational and binding flexibility. Individual tartrate structures exhibit many different architectures and physical properties, such as chirality, porosity, magnetism, luminescence and dielectricity. Indeed, the first known ferroelectric material, Rochelle’s Salt, whose crystal structure was first determined in 1940, is a potassium sodium tartrate framework: KNa(C4H4O6)·4H2O. [2]